Nonbenzenoid compounds



Patented Aug. 6, 1946 NONBENZENOID COMPOUNDS Lewis W. Butz, Beltsville, Md., assignor to the United States of America, as represented by the Secretary of Agriculture NoDrawingz- Original application December 12,

1942, Serial No. 468,795. Divided and this application July 10, 1945, Serial No. 604,289

1 Claim.

(Granted under the act of March 3, 1883, as amended April 30, 1928; 370 0. G. 757) This application is made under the act of March 3, 1883, as amended by the act of April 30,

four rings of carbon atoms having substantially the structure:

1928, and the invention herein described and claimed, if patented, may be manufactured and B used by or for the Government of the United 5 States of America for governmental purposes CHCH without the payment to me of any royalty 0 0 CH2 thereon. on, o (f Cz This application is a division of my copending l I I application for patent Serial No. 468,795, filed f5 f5 December 12, 1942. CH 00 My invention relates to non-benzenoid fused polycyclic organic compounds and to processes for preparing them.

I have found that organic compounds belonging to the class of 1,5-diene-3-ynes, i. e., compounds containing the atomic grouping react with two moles of dienophilic compounds containing the atomic grouping This is non-benzenoid steroid. It possesses the seventeen-carbon four-ring skeleton common to all the steroids which have been found in organic materials. Furthermore, it is a steroid containing only hydrogenated rings and one novel feature of the process'is its capacity to yield polycyclic compounds lacking any aromatic (benzenoid) ring. All known processes for the synthesis of steroids relate to the preparation of benzenoid steroids. But the majority of the naturally occurring steroids, among them the therapeutically important male hormones, adrenocortical hormones, and progesterone are non-benzenoids My process makes available, for th first time, by synthesis, steroids of the non-benzenoid type, as well as non-steroid types of polycyclic compounds, which are useful as intermediates in the synthesis of therapeutic compounds.

The following example for the preparation of 1 methyl 5,6 propano-2,3,4,6,7,8 hexahydronaphthalene-3,4,7,S-tetracarboxylic-3,4;7,8-dianhydride will illustrate my invention more fully.

One molecular proportion of cyclopentenyliso- 011-4311, propenylacetylene was added to two molecular E= proportions of maleic anhydride in an open vessel on, c o 011, 40 at C. while passing a stream of carbon diox- J g ide to exclude air. The mixture was heated at \CH -160 C. for two hours. Volatile components reacts readily with maleic anhydride. By this reaction, there is formed a compound containing were then removed by fractional distillation. The residue was dissolved in ethyl acetate and ether was added, resulting in the precipitation of an amorphous material. This amorphous material was separated. Part of the ether and ethyl acetate was evaporated and th solution was set aside to crystallize. After seven days, crystals formed which were separated and recrystallized from benzene-petroleum ether. The crystalline product is represented by the following structural formula:

and its empiric composition is CHI-1140s. The presence of tw conjugated double bonds spread over two rings is substantiated by absorption spectrum data.

Having thus described my invention, I claim:

The 1 methy15,6-propano-2,3,4,6,7,8-hexahydronaphthalene 3,4,7,8 tetracarboxylic-3,4;7,8- dianhydride, having substantially the structure:

O-GO CHE-CE? LEWIS W. BUTZ. 

